Protein cross-linked with phosphonitrilic halide

ABSTRACT

IMPROVED PROTEIN FEED MATERIAL FOR RUMINANTS WHICH IS RESISTANT TO DIGESTIVE BREAKDOWN IN THE RUMEN BUT NOT IN THE ABOMASUM AND/OR INTESTINES WHICH COMPRISES THE REACTION PRODUCT OF A PROTEIN-CONTAINING FEED MATERIAL AND A PHOSPHONITRILIC HALIDE. EXEMPLARY OF SUCH PHOSPHONITRILLIC HALIDES IS PHOSPHONITRILLIC CHLORIDE TRIMER.

United States Patent O 3,674,509 PROTEIN CROSS-LINKED WITH PHOSPHO- NITRILIC HALIDE Robert E. Miller, Ballwin, Mo., assignor to Monsanto Company, St. Louis, M0. N Drawing. Filed Oct. 27, 1970, Ser. No. 84,479 Int. Cl. A233 3/00; A23k N18 US. Cl. 99-2 N 8 Claims ABSTRACT OF THE DISCLOSURE Improved protein feed material for ruminants which is resistant to digestive breakdown in the rumen but not in the abomasum and/or intestines which comprises the reaction product of a protein-containing feed material and a phosphonitrilic halide. Exemplary of such phosphonitrilic halides is phosphonitrilic chloride trimer.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a method for improving the feed utilization of ruminant animals. In a particular aspect this invention relates to a method for improving protein utilization in ruminant animals. In a further aspect this invention relates to modified protein feed compositions useful in ruminant nutrition which are resistant to digestive attack in the fluid medium of the rumen.

DESCRIPTION OF THE PRIOR ART The digestive system of the ruminant animal (cattle, sheep, bison, camels, etc.) is designed to permit eflicient use of coarse, fibrous foodstuffs. Because of its particular structure and nature, however, the ruminants digestive system is inefficient in obtaining nutritional value from protein materials. Principally for this reason it is common practice in ruminant nutrition to supplement the diet of the animal with added protein. The supplemental protein serves to increase the rate of growth of the animal and in the case of sheep promotes wool growth.

The rumen, the largest of the four stomach compartments of the animal, serves as an important location for digestive breakdown or ingested foodstufis chiefly through the action of microorganisms present therein. However, absorption of most nutrients for metabolic purposes does not occur in the rumen but takes place further along in the alimentary tract, principally in the abomasum and intestines. Ingested food is typically retained in the rumen for from about 12-30 hours during which time it is subject to digestive breakdown by the microorganisms and by the rumen fluid. Much ingested protein material is broken down in the rumen to soluble peptides and amino acids. In turn much of these peptides and amino acids are utilized by the microorganisms present in the rumen fluid thereby removing them as a source of nutrition for the host animal.

Because of the desirability as indicated above of avoiding protein breakdown in the rumen in order to permit absorption in the abomasum and intestines it has been suggested that nutrient protein-containing materials fed to ruminants be treated so as to permit passage without digestive breakdown through the rumen to the abomasum. Suggested procedures have included coating the protein material, for example, with fats and vegetable oils, heat 3,6745% Patented July 4, 1972 Ice treatment of the protein material and reaction of the protein material with formaldehyde. In any event the treated material must be resistant to digestive breakdown in the rumen fluid, which is a fluid buttered at about pH 6-7 by phosphate-bicarbonate from saliva and carbon dioxide, but subject to breakdown in the acid medium of the fluid of the abomasum which has a pH, due principally to hydrochloric acid secretion, of about 2-4.

OBJECTS It is an object of the present invention to provide a method for improving the feed utilization of ruminant animals.

It is a further object of the present invention to provide a method for improving the protein utilization of ruminant animals whereby protein passes through the rumen without substantial digestive breakdown.

Other objects and advantages of the present invention will be apparent from the specification and appended claims.

SUMMARY OF THE INVENTION It has been found in accordance with the present invention that the protein utilization of the ruminant animal is improved by feeding the animal a reaction product of a protein-containing nutrient material and a phosphonitrilic halide trimer.

The amount of phosphonitrilic halide in the reaction product is sufficient to prevent substantial digestive breakdown in the fluid medium of the rumen but insuflicient to prevent digestive breakdown in the fluid media of the abomasum and of the intestines.

DETAILED DESCRIPTION The protein-containing reaction product used in the method of the present invention is the reaction product of a protein-containing nutrient feed material and a phosphonitrilic halide. Suitable phosphonitrilic halides useful in the process of the present invention are represented by the following general formula wherein X is a halo radical, for example, chloro, bromo, and iodo. Suitable phosphonitrilic halides include phosphonitrilic chloride trimer, phosphonitrilic bromide trimer, and phosphonitrilic iodide trimer.

The protein-containing nutrient material can be from any suitable source including animal, plant, or synthetic sources such as, for example, silage, grains, nuts, chaffs, casein, soy bean meal, fish meal, peanut meal, beef scraps, pork scraps, linseed meal, milk solids, etc.

The useful reaction products of the present invention are prepared by the interaction of phosphonitrilic halide and protein nutrient material by any suitable procedure. The reaction is readily carried out in a suitable solvent medium inert to the reactants and the reaction products. Such suitable inert solvents include basic solvents, for example, piperidine, N-methyl morpholine, and non-polar organic solvents containing an organic base such as triethylene diamine. The reaction may be carried out at any suitable temperature and is preferably carried out at from about 50 to about 70 C. for from about 1 to about 4 hrs. However, elevated temperatures above about 70 C. particularly for extended periods should be avoided to minimize degradation of protein material. Temperatures in the range of from about to about 40 C. are typically employed with room temperature being both suitable and practical. The reaction is preferably carried out simply by forming a slurry of the reactants in the solvent medium and agitating, as by stirring, the slurry thereby to permit suflicient reaction of the protein with the phosphonitrilic halide. The thus treated protein is then dried as by oven drying, drum drying, or simple evaporation to recover the modified protein nutrient material.

The phosphonitrilic halide-protein product of the present invention in addition to providing a useful source of protein for the ruminant animal serves to provide a source of assimilable phosphorous for the animal.

It is important in order to insure operability of the present invention that the amount of phosphonitrilic halide incorporated into the protein be sufficient to prevent digestive breakdown to soluble peptides and amino acids in the rumen but insuflicient to prevent digestive breakdown to soluble peptides and amino acids in the abomasum and intestines. This amount will, of course, vary and will depend among other things on the particular protein material, the particular phosphonitrilic halide of choice, the pH of the solvent of reaction, time and temperature of reaction, the species and age of the animal, and the total makeup of the animal diet. Typically an amount in the range of from about 0.0005 to about 0.01 mole of phosphonitrilic halide for each gram of protein contained in the protein material is employed with amounts in the range of from about 0.0002 to about 0.001 mole being generally preferred.

It is to be understood that the modified ruminant protein feed of the present invention can be fed sep arately to the animal or it can be used for incorporation in other ruminant feed materials. Illustrative of ruminant feed materials in which the protein material of the present invention may be incorporated are soybean meal, ground corn, hay, straw, cotton seed hulls, cotton mill waste, feed pulp, silage, oats, barley, cereal, brans, cereal middlings and combinations thereof. If desired other components, for example, minerals, such as bone meal, salt, and trace minerals, antibiotics and vitamins may be included in the animal feed ration.

The following examples illustrate the eifectiveness of phosphonitrilic halide compositions useful in the present invention in protecting protein-containing material from digestion in the fluid of the rumen While permitting digestion in the fluids of the abomasum and intestines. The small scale in vitro experiments shown in the examples simulate conditions existing in the rumen, in the abomasum and in the intestines thereby permitting the study of treated protein without the use of the live animal and large quantities of feed materials. It is understood that the examples are presented for the purpose of illus tration only and the invention is not limited to the compositions or methods shown therein.

EXAMPLE 1 Preparation of treated protein Casein (4.99 grams) was added to a solution of phosphonitrilic chloride trimer (0.49 gram) in pyridine (25 milliliters). The resulting mixture was stirred for about 1 hour at 70 C. to permit reaction of the phosphonitrilic halide with the casein. The reaction product was filtered, washed with acetone and vacuum dried to obtain protein product-containing 0.0002 mole of phos phonitrilic chloride trimer per gram of casein.

R-umen digestion test To 10 milliliters of rumen fluid from fasted sheep contained in a 50 milliliter glass flask was added 10 milliliters of a buffered solution of the following composition.

Bufier solution in grams per liter The resulting mixture was adjusted to pH 6.8 (4 N hydrochloric acid). To the buttered rumen fluid was added milligrams of the phosphonitrilic chloride trimer treated protein prepared above. The flask was then purged with nitrogen, stoppered (pressure release valve) and heated at 38 C. on a water shaker bath. Protection of protein from digestion was determined by ammonia production with a lower amount of ammonia production indicating a lower amount of digestion of protein. Ammonia production was determined after 6 hours and after 25 hours with results being presented in Table 1.

Abomasum digestion test Gastric fluid was prepared as follows: NaCl (2 grams) was dissolved in suflicient water to give a total volume of 950 milliliters. Pepsin (3.2 grams) was added thereto. Concentrated hydrochloric acid (7 milliliters) was added to the resulting medium and the pH of the medium was then adjusted to 2.0 with aqueous sodium hydroxide.

To a glass flask containing 20 milliliters of the gastric fluid were added 60 milligrams of phosphonitrilic chloride treated casein prepared above. The glass flask containing the resulting mixture was stoppered with pressure release valves and heated at 38 C. on a water shaker bath for 2 hours. Digestion of protein was then determined by ammonia analysis, the greater amount of ammonia produced the greater the amount of protein digested. The results are given in Table l.

Intestine digestion test Intestinal fluid was prepared as follows: NaCl (2 grams) was dissolved in suflicient water to give a total volume of 950 milliliters. Pepsin (3.2 grams) was added thereto. Concentrated hydrochloric acid (7 milliliters) was added to the medium and the pH of the medium was then adjusted to 7.0 with 0.1 N sodium hydroxide. Pancreatin (10 milligrams per milliliter of medium) Was added to the resulting medium.

To a glass flask containing 20 milliliters of the in testinal fluid were added 60 milligrams of phosphonitrilic chloride trimer treated casein prepared above. The glass flask was stoppered with pressure release valves and heated at 38 C. on a water shaker bath, for the prescribed period of time. Digestion of protein was determined by ammonia analysis, the greater amount of ammonia produced the greater amount of protein digested. The results are given in Table 1.

EXAMPLES 2-9 Following the general procedures and tests of Example 1 phosph'onitrilic chloride treated casein samples were prepared and tested. The results are given in Table 1.

In the same manner other protein containing materials may be reacted with phosphonitrilic halides to protect the protein material from digestive breakdown in the rumen while permitting its digestion in the abornasum.

EXAMPLE 1o Phosphonitrilic bromide treated casein containing 0.0002 mole phosphonitrilic bromide per gram of protein is resistant to digestion in the rumen but is readily digested in the abomasum.

Since many embodiments of this invention may be made and since many changes may be made in the embodiments described, the foregoing is to be interpreted as illustrative only and the invention is defined by the claims appended hereto.

TABLE 1 Percent total protein digested 1 Due at least in part to decomposition of rumen microorganisms.

I claim:

1. A method for improving the protein utilization of ruminant animals which comprises feeding the ruminant animal the reaction product of a protein-containing nutrient feed material and a phosphonitrilic halide trimer to cross-link the protein, the amount of phosphonitrilic halide trimer in said reaction product being sufficient to render said feed material resistant to digestive breakdown in the fluid of the rumen but insufficient to prevent substantial digestive breakdown in the fluids of the abomasum and of the intestines.

2. The method of claim 1 wherein the phosphonitrilic halide trimer is phosphonitrilic chloride trimer.

3. The method of claim 1 wherein the amount of phosphonitrilic halide in the reaction product is in the range of from about 0.0005 to about 0.01 mole per gram of protein.

4. The method of claim 3 wherein the amount of phosphonitrilic halide trimer is in the range of from about 0.0002 to about 0.001 mole per gram of protein.

5. An animal feed composition comprising the reaction product of a protein-containing nutrient feed material and a phosphonitrilic halide, the amount of phosphonitrilie halide in said reaction product being sufficient to render said feed material resistant to digestive breakdown in the fluid of the rumen but insuflicient to prevent substantial digestive breakdown in the fluids of the *abomasum and of the intestines.

6. The composition of claim 5 wherein the phosphonitrilic halide is phosphonitrilic chloride.

7. The composition of claim 5 wherein the amount of phosphonitrilic halide is in the range of from about 0.0005 to about 0.01 mole per gram of protein.

8. The composition of claim 7 wherein the amount of phosphonitrilic halide is in the range of from about 0.0002 to about 0.001 mole per gram of protein.

References Cited UNITED STATES PATENTS 1/1968 Allcock et al. 260-30.2

OTHER REFERENCES NORMAN YUDKOFF, Primary Examiner C. P. RlBANDO, Assistant Examiner UJS. Cl. X.R.

99-2 R, 14; 260-l 12 R, 119, 123.5 

